Electron Donor-Acceptor Complex-Initiated Photochemical Cyanation for the Preparation of α-Amino Nitriles

An electron donor-acceptor complex-initiated alpha-cyanation of tertiary amines has been described. The reaction protocol provides a novel method to synthesize various alpha-amino nitriles under mild conditions. The reaction can proceed smoothly without the presence of photocatalysts and transition metal catalysts, and either oxidants are unnecessary or O-2 is the only oxidant. The practicality of this method is showcased not only by the late-stage functionalization of natural alkaloid derivatives and pharmaceutical intermediate, but also by the applicability of a stop-flow microtubing reactor.